EP2488501B1 - Neue mikrobiozide - Google Patents

Neue mikrobiozide Download PDF

Info

Publication number
EP2488501B1
EP2488501B1 EP10765439.4A EP10765439A EP2488501B1 EP 2488501 B1 EP2488501 B1 EP 2488501B1 EP 10765439 A EP10765439 A EP 10765439A EP 2488501 B1 EP2488501 B1 EP 2488501B1
Authority
EP
European Patent Office
Prior art keywords
formula
hydrogen
methyl
alkyl
compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
EP10765439.4A
Other languages
English (en)
French (fr)
Other versions
EP2488501A1 (de
Inventor
Harald Walter
Daniel Stierli
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Syngenta Participations AG
Original Assignee
Syngenta Participations AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Syngenta Participations AG filed Critical Syngenta Participations AG
Priority to EP10765439.4A priority Critical patent/EP2488501B1/de
Publication of EP2488501A1 publication Critical patent/EP2488501A1/de
Application granted granted Critical
Publication of EP2488501B1 publication Critical patent/EP2488501B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
    • C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
    • C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
    • C07D231/14—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C239/00—Compounds containing nitrogen-to-halogen bonds; Hydroxylamino compounds or ethers or esters thereof
    • C07C239/08—Hydroxylamino compounds or their ethers or esters
    • C07C239/20—Hydroxylamino compounds or their ethers or esters having oxygen atoms of hydroxylamino groups etherified
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D333/00—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom
    • C07D333/02—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings
    • C07D333/04—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom
    • C07D333/26—Heterocyclic compounds containing five-membered rings having one sulfur atom as the only ring hetero atom not condensed with other rings not substituted on the ring sulphur atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D333/28—Halogen atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D409/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms
    • C07D409/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings
    • C07D409/12—Heterocyclic compounds containing two or more hetero rings, at least one ring having sulfur atoms as the only ring hetero atoms containing two hetero rings linked by a chain containing hetero atoms as chain links

Definitions

  • the present invention relates to novel microbiocidally active.
  • fungicidally active carboxamides.
  • Fungicidally active carboxamides are described in WO 2007/134799 .
  • the present invention accordingly relates to N-alkoxycarboxamides of formula I wherein
  • the invention covers all agrochemically acceptable salts/ stereoisomers/diastereoisomers/enantiomers/tautomers and N-oxides of those compounds.
  • alkyl groups occurring in the definitions of the substituents can be straight-chain or branched and are, for example, methyl, ethyl, n -propyl, n -butyl, n -pentyl, n -hexyl, iso -propyl, n- butyl, sec -butyl, iso -butyl or tert -butyl
  • alkenyl and alkynyl radicals are derived from the alkyl radicals mentioned
  • the alkenyl and alkynyl groups can be mono- or di-unsaturated.
  • cycloalkyl groups occuring in the definitions of the substituents are, for example, cyclopropyl, cyclobutyl, cyclopentyl or cyclohexyl.
  • Halogen is generally fluorine, chlorine, bromine or iodine, preferably fluorine, bromine or chlorine This also applies, correspondingly, to halogen in combination with other meanings, such as halogenalkyl or halogenalkoxy.
  • Haloalkyl groups preferably have a chain length of from 1 to 4 carbon atoms.
  • Halonalkyl is, for example, fluoromethyl, difluoromethyl, trifluoromethyl, chloromethyl, dichloromethyl, trichloromethyl, 2,2,2-trifluoroethyl, 2-fluoroethyl, 2-chloroethyl, pentafluoroethyl, 1,1-difluoro-2,2,2-trichloroethyl, 2,2,3,3-tetrafluoroethyl and 2,2,2-trichloroethyl; preferably trichloromethyl, difluorochloromethyl, difluoromethyl, trifluoromethyl and dichlorofluoromethyl.
  • Alkoxy is, for example, methoxy, ethoxy, propoxy, i-propoxy, n-butoxy, isobutoxy, sec-butoxy and tert-butoxy, preferably methoxy and ethoxy.
  • Halogenalkoxy is, for example, fluoromethoxy, difluoromethoxy, trifluoromethoxy, 2,2,2-trifluoroethoxy, 1,1,2,2-tetrafluoroethoxy, 2-fluoroethoxy, 2-chloroethoxy, 2,2-difluoroethoxy and 2,2,2-trichloroethoxy; preferably difluoromethoxy, 2-chloroethoxy and trifluoromethoxy.
  • R 1 is C 1 -C 4 haloalkyl
  • R 2 is C 1 -C 4 akyl
  • R 3 is hydrogen
  • R 4 is C 1 -C 4 alkyl
  • R 5 is hydrogen or C 1 -C 4 alkyl
  • R 9 is hydrogen
  • R 7 is hydrogen, C 1 -C 4 alkyl or halogen
  • R 8 is hydrogen, C 1 -C 4 alkyl or halogen
  • R 9 is hydrogen, C 1 -C 4 alkyl or halogen
  • R 10 is hydrogen, C 1 -C 4 alkyl or halogen
  • R 11 , R 12 and R 13 are, independently from each other, hydrogen or halogen.
  • R 5 is methyl
  • At least one of R 11 , R 12 and R 13 is halogen.
  • R 1 is difluoromethyl;
  • R 2 is methyl;
  • R 3 is hydrogen;
  • R 4 is methyl;
  • R 5 is hydrogen or methyl;
  • R 6 is hydrogen;
  • R 7 is hydrogen, methoxy or chloro; and
  • R 8 , R 9 and R 10 are hydrogen;
  • Particularly preferred compounds of formula I are those, wherein R 1 is difluoromethyl or trifluoromethyl; R 2 is methyl; R 3 is hydrogen; R 4 is methyl; R 5 is hydrogen, methyl or ethyl; and R 6 , R 7 , R 8 , R 9 and R 10 are hydrogen.
  • R 1 is C 1 -C 4 haloalkyl
  • R 2 is C 1 -C 4 alkyl
  • R 3 is hydrogen
  • R 4 is C 1 -C 4 alkyl
  • R 5 is C 1 -C 4 alkyl
  • R 6 , R 7 , R 8 , R 9 and R 10 are hydrogen
  • B is a phenyl or thienyl group, which groups are substituted by R 11 , R 12 and R 13 ; and R 11 , R 12 and R 13 are, independently from each other, hydrogen or halogen.
  • Compounds of formula I may be prepared by reacting a compound of formula II wherein R 4 , R 5 , R 6 , R 7 , R 8 , R 9 , R 10 , and B are as defined under formula I; with a compound of formula III in which R 1 , R 2 and R 3 are as defined under formula I, and R* is halogen, hydroxy or C 1-6 alkoxy, preferably chloro.
  • aprotic inert organic solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone.
  • hydrocarbons such as benzene, toluene, xylene or cyclohexane
  • chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene
  • ethers such as diethyl
  • the reaction temperatures are advantageously between -20°C and +120°C.
  • the reactions are slightly exothermic and, as a rule, they can be carried out at ambient temperature.
  • the mixture may be heated briefly to the boiling point of the reaction mixture.
  • the reaction times can also be shortened by adding a few drops of base as reaction catalyst.
  • Suitable bases are, in particular, tertiary amines such as trimethylamine, triethylamine, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene.
  • inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases.
  • the bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example a crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • a coupling agent such as benzotriazol-1-yloxytris(dimethylamino) phosphoniumhexafluorophosphate, bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride (BOP-Cl), N,N'-dicyclohexylcarbodiimide (DCC) or 1,1'-carbonyl-diimidazole (CDI), may be used.
  • BOP-Cl bis-(2-oxo-3-oxazolidinyl)-phosphinic acid chloride
  • DCC N,N'-dicyclohexylcarbodiimide
  • CDI 1,1'-carbonyl-diimidazole
  • R 4 , R 5 , R 7 , R 8 , R 9 , R 10 and B are as defined under formula I, may be prepared as described in reaction scheme 1.
  • Oxime ether derivatives of formula VI in which and R 4 , R 5 , R 7 , R 8 , R 9 , R 10 and B are as defined under formula I may be prepared by oximation of ketones or aldehydes of formula IV with O-alkyl hydroxylamine derivatives of formula V or a salt thereof.
  • Suitable solvents carrying out the oximation step are hydrocarbons such as benzene, toluene, xylene or cyclohexane, chlorinated hydrocarbons such as dichloromethane, trichloromethane, tetrachloromethane or chlorobenzene, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, nitriles such as acetonitrile or propionitrile, amides such as N,N-dimethylformamide, diethylformamide, N-methylpyrrolidinone, alcohols such as methanol, ethanol, n-propanol,i-propanol, n-butanol, sec.butanol water or mixtures.
  • hydrocarbons such as benzene, toluene, xylene or cyclohexane
  • the reaction temperatures are advantageously between -20°C and +120°C.
  • the reactions can be carried out at ambient temperature.
  • Suitable bases are, in particular pyridine, tertiary amines such as trimethylamine, triethylamine, huenig base, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene.
  • inorganic bases such as hydroxides, e.g. sodium hydroxide or potassium hydroxide, carbonates such as sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases.
  • oxime ether derivatives of formula VI may be prepared by O-alkylation of oxime derivatives of formula VIb with a compound of formula VII, in which R 4 is C 1 -C 4 alkyl or C 1 -C 4 halogenalkyl and X represents a leaving group, such as halogen, mesylate or tosylate, in the presence of a base.
  • the alkylation reaction is advantageously carried out in aprotic inert organic solvents.
  • Such solvents are hydrocarbons such as benzene, toluene, xylene or cyclohexane, ethers such as diethyl ether, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, tetrahydrofuran or dioxane, amides such as N,N-dimethylformamide, diethylformamide or N-methylpyrrolidinone.
  • the reaction temperatures are between -20°C and +120°C.
  • Suitable bases are inorganic bases such as hydrides, e.g. sodium hydride or calcium hydride, hydroxides, e.g.
  • the bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • the oximes of formula Vlb can be obtained by reacting aldehyde or ketone IV with hydroxylamine hydrochloride from room temperature to reflux, preferably at room temperature, in an appropriate solvent such as methanol or ethanol in the presence of an appropriate alkali such as sodium hydroxide, potassium carbonate or pyridine.
  • O-Alkylhydroxylamines of formula IIA may be prepared by the reduction of O-alkoxy oxime derivatives of formula VI. It will be appreciated by those skilled in the art that this reduction can be carried out with a number of different reducing agents.
  • O-Alkylhydroxylamines of formula IIA may also prepared by the nucleophilic substitution of derivatives of formula VII in which R 5 , R 7 , R 8 , R 9 and R 10 are as defined under formula I and X represents a leaving group, such as halogen, mesylate or tosylate, with a compound of formula V, in which R 4 is C 1 -C 4 alkyl or C 1 -C 4 halogenalkyl, in the presence of a base.
  • the substitution reaction is advantageously carried out in aprotic inert organic solvents. The reaction temperatures are between 0°C and +100°C.
  • Suitable bases are, in particular pyridine, tertiary amines such as trimethylamine, triethylamine, huenig base, quinuclidine, 1,4-diazabicyclo[2.2.2]octane, 1,5-diazabicyclo[4.3.0]non-5-ene or 1,5-diazabicyclo[5.4.0]undec-7-ene.
  • inorganic bases such as carbonates, sodium carbonate and potassium carbonate, or hydrogen carbonates such as potassium hydrogen carbonate and sodium hydrogen carbonate may also be used as bases.
  • the bases can be used as such or else with catalytic amounts of a phase-transfer catalyst, for example crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • a phase-transfer catalyst for example crown ether, in particular 18-crown-6, or a tetraalkylammonium salt.
  • R 5 , R 7 , R 8 , R 9 and R 10 are as defined under formula I, may be prepared as described in reaction scheme below.
  • the diastereomers can be separated either chromatographically or, after saponification, by recrystallisation of the corresponding carboxylic acids of formula XII, wherein R 1 , R 2 , R 3 , R 4 and B are as defined under formula II.
  • Said carboxylic acids can be converted to the corresponding Weinreb amide of formula XIII, wherein R 7 , R 8 , R 9 , R 10 and B are as defined under formula II using N,O-dimethylhydroxylamine hydrochloride with a coupling reagent like EDC in the presence of a suitable base like N-methylmorpholine in an appropriate solvent such as dichloromethane.
  • the Weinreb amide of formula XIII can be converted to the corresponding ketones of formula VI using Grignard reagents R 5 MgX or organolithium reagents R 5 Li addition of formula XIV, wherein R 5 is defined as under formula II in an inert solvent like THF at a suitable temperature.
  • the cyclopropanation is carried out at temperatures of between 0 - 100°C in a convenient organic solvent such as methanol, ethanol, tert-butanol, trifluoroethanol, chloroform, dichloromethane or dioxane.
  • a convenient organic solvent such as methanol, ethanol, tert-butanol, trifluoroethanol, chloroform, dichloromethane or dioxane.
  • the cyclopropyl aldehydes or ketones VI may also be prepared by conventional techniques.
  • the unsaturated aldehyde or ketone XVI is reacted with a sulfur ylide of formula XVIII, prepared from a dimethylsulfoxonium salt in the presence of a base, resulting the substituted cyclopropanes VI.
  • a sulfur ylide of formula XVIII prepared from a dimethylsulfoxonium salt in the presence of a base, resulting the substituted cyclopropanes VI.
  • the chemistry of sulfur ylides was developed by Corey and Chaykovsky and is described in Trost and Melvin, Sulfur Ylids, Acd. Press, NY 1975 and in Block, Reactions of Organosulfur Compounds, pp.91-123 Acd. Press, NY 1978 .
  • Typical reaction conditions for sulfur ylide formation from dimethylsulfoxonium salt utilizes bases such as hydroxides, metal hydrides and alkoxides in solvents such as dimethoxyethane, dimethylsulfoxide and water deepending on the base employed.
  • bases such as hydroxides, metal hydrides and alkoxides in solvents such as dimethoxyethane, dimethylsulfoxide and water deepending on the base employed.
  • the reaction conducted from 0-20°C preferably from 10-15°C and preferably with alkali metal hydroxides in dimethylsulfoxide.
  • dimethylsulfoxonium methylide is prepared from trimethylsulfoxonium iodide in dimethylsulfoxide in the presence of powdered sodium hydroxide at room temperature.
  • the ⁇ , ⁇ -unsaturated aldehydes or ketones of formula XVII may prepared by conventional condensation techniques.
  • Aryl or heteroaryl aldehydes of formula XV where R 8 is hydrogen and B is defined under formula II are reacted with the ketones of formula XVI to provide the intermediates of formula XVII.
  • the ketone XVI is dissolved in a protic solvent such as methanol or ethanol, to which is added dropwise the aldehyde B, followed by the base.
  • the reaction temperatures are between 0°C and +35°C.
  • Suitable bases are inorganic bases such as hydroxides, e.g. barium hydroxide, sodium hydroxide or potassium hydroxide.
  • the solvent can be acetone.
  • the aldehyde is dissolved in a mixture of acetone: water (1:5) to which is added the base while stirring at room temperature.
  • compounds of formula XVII may be prepared according to the procedure described in US Patent Number 3,950,427 , col.17 line 20, to provide after purification the E diastereomere (B is trans to R 8 CO).
  • ketone of formula XV is reacted with an ethyl trans 3-ethoxycrotonate of formula XIX in DMF in the presence of potassium t-butoxyde to form the intermediate of formula XX, to give after acidic hydrolysis and decarboxylation XVII.
  • the crotonates of formula XIX may be prepared from substituted acetoketones of formula XXI by conventional techniques.
  • XVII can be prepared by a Heck reaction of a halide XXV with an acryl ketone of formula XXVI.
  • the cyclopropyl aldehydes or ketones of formula VI can be prepared from cyclopropyl nitriles of formula XXII which are prepared via cyclopropanation of the acrylonitriles of formula XXIII.
  • the acrylonitriles of formula XXIII may be prepared by conventional synthetic methods as described in March, Advanced Organic Chemistry, 4th Ed, pp.937-955 and references therein.
  • the nitrile derivative of formula XXIV is condensed with the ketone or aldehyde of formula XVI in the presence of a base to provide the acrylonitrile XXIII.
  • a nitrile of formula XXIV is dissolved in a solvent such as ethanol and water to which is added the aldehyde or ketone of formula XV followed by a base.
  • the reaction temperature is typically at ambient temperature.
  • Suitable bases are alkali hydroxides such as barium hydroxide, sodium hydroxide or potassium hydroxide.
  • the cyclopropyl nitrile of formula XXII is transformed to the cyclopropyl ketone VI by organometallic addition to the nitrile followed by hydrolysis.
  • Standard Grignard reagents R 5 MgX or organolithium reagents R 5 Li add to the nitrile functionality to provide the ketone VI.
  • Cyclopropyl nitrile can be transformed to cyclopropyl aldehyde of formula VI where R 5 is hydrogen by standard reductive methods such as with Diisobutylaluminium hydride (DIBALH).
  • DIBALH Diisobutylaluminium hydride
  • the compounds I and, where appropriate, the tautomers thereof, can, if appropriate, also be obtained in the form of hydrates and/or include other solvents, for example those which may have been used for the crystallization of compounds which are present in solid form.
  • the invention therefore also relates to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a compound of formula I is applied as active ingredient to the plants, to parts thereof or the locus thereof.
  • the compounds of formula I according to the invention are distinguished by excellent activity at low rates of application, by being well tolerated by plants and by being environmentally safe. They have very useful curative, preventive and systemic properties and are used for protecting numerous useful plants.
  • the compounds of formula I can be used to inhibit or destroy the diseases that occur on plants or parts of plants (fruit, blossoms, leaves, stems, tubers, roots) of different crops of useful plants, while at the same time protecting also those parts of the plants that grow later e.g. from phytopathogenic microorganisms.
  • compounds of formula I as dressing agents for the treatment of plant propagation material, in particular of seeds (fruit, tubers, grains) and plant cuttings (e.g. rice), for the protection against fungal infections as well as against phytopathogenic fungi occurring in the soil.
  • the compounds of formula I according to the invention may be used for controlling fungi in related areas, for example in the protection of technical materials, including wood and wood related technical products, in food storage or in hygiene management.
  • the compounds of formula I are, for example, effective against the phytopathogenic fungi of the following classes: Fungi imperfecti (e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria) and Basidiomycetes (e.g. Rhizoctonia, Hemileia, Puccinia). Additionally, they are also effective against the Ascomycetes classes (e.g. Venturia and Erysiphe, Podosphaera, Monilinia, Uncinula) and of the Oomycetes classes (e.g. Phytophthora, Pythium, Plasmopara).
  • Fungi imperfecti e.g. Botrytis, Pyricularia, Helminthosporium, Fusarium, Septoria, Cercospora and Alternaria
  • Basidiomycetes e.g. Rhizoctonia, Hemileia, Puccinia
  • novel compounds of formula I are effective against phytopathogenic bacteria and viruses (e.g. against Xanthomonas spp, Pseudomonas spp, Erwinia amylovora as well as against the tobacco mosaic virus). Good activity has been observed against Asian soybean rust (Phakopsora pachyrhizi).
  • useful plants to be protected typically comprise the following species of plants: cereal (wheat, barley, rye, oat, rice; maize, sorghum and related species); beet (sugar beet and fodder beet); pomes, drupes and soft fruit (apples, pears, plums, peaches, almonds, cherries, strawberries, raspberries and blackberries); leguminous plants (beans, lentils, peas, soybeans); oil plants (rape, mustard, poppy, olives, sunflowers, coconut, castor oil plants, cocoa beans, groundnuts); cucumber plants (pumpkins, cucumbers, melons); fibre plants (cotton, flax, hemp, jute); citrus fruit (oranges, lemons, grapefruit, mandarins); vegetables (spinach, lettuce, asparagus, cabbages, carrots, onions, tomatoes, potatoes, paprika); lauraceae (avocado, cinnamomum, camphor) or plants such as tobacco
  • useful plants is to be understood as including also useful plants that have been rendered tolerant to herbicides like bromoxynil or classes of herbicides (such as, for example, HPPD inhibitors, ALS inhibitors, for example primisulfuron, prosulfuron and trifloxysulfuron, EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors, GS (glutamine synthetase) inhibitors or PPO (protoporphyrinogen-oxidase) inhibitors) as a result of conventional methods of breeding or genetic engineering.
  • herbicides like bromoxynil or classes of herbicides
  • EPSPS (5-enol-pyrovyl-shikimate-3-phosphate-synthase) inhibitors
  • GS glutamine synthetase
  • PPO protoporphyrinogen-oxidase
  • imazamox by conventional methods of breeding (mutagenesis) is Clearfield® summer rape (Canola).
  • crops that have been rendered tolerant to herbicides or classes of herbicides by genetic engineering methods include glyphosate- and glufosinate-resistant maize varieties commercially available under the trade names RoundupReady®, Herculex I® and LibertyLink®.
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising one or more selectively acting toxins, such as are known, for example, from toxin-producing bacteria, especially those of the genus Bacillus.
  • YieldGard® (maize variety that expresses a CryIA(b) toxin); YieldGard Rootworm® (maize variety that expresses a CryIIIB(B 1 ) toxin); YieldGard Plus® (maize variety that expresses a CryIA(b) and a CryIIIB(B 1 ) toxin); Starlink® (maize variety that expresses a Cry9(c) toxin); Herculex I® (maize variety that expresses a CryIF(a2) toxin and the enzyme phosphinothricine N-acetyltransferase (PAT) to achieve tolerance to the herbicide glufosinate ammonium); NuCOTN 33B® (cotton variety that expresses a CryIA(c) toxin); Bollgard I® (cotton variety that expresses a CryIA(c) toxin); Bollgard II® (
  • useful plants is to be understood as including also useful plants which have been so transformed by the use of recombinant DNA techniques that they are capable of synthesising antipathogenic substances having a selective action, such as, for example, the so-called "pathogenesis-related proteins" (PRPs, see e.g. EP-A-0 392 225 ).
  • PRPs pathogenesis-related proteins
  • Examples of such antipathogenic substances and transgenic plants capable of synthesising such antipathogenic substances are known, for example, from EP-A-0 392 225 , WO 95/33818 , and EP-A-0 353 191 .
  • the methods of producing such transgenic plants are generally known to the person skilled in the art and are described, for example, in the publications mentioned above.
  • locus of a useful plant as used herein is intended to embrace the place on which the useful plants are growing, where the plant propagation materials of the useful plants are sown or where the plant propagation materials of the useful plants will be placed into the soil.
  • An example for such a locus is a field, on which crop plants are growing.
  • plant propagation material is understood to denote generative parts of the plant, such as seeds, which can be used for the multiplication of the latter, and vegetative material, such as cuttings or tubers, for example potatoes. There may be mentioned for example seeds (in the strict sense), roots, fruits, tubers, bulbs, rhizomes and parts of plants. Germinated plants and young plants which are to be transplanted after germination or after emergence from the soil, may also be mentioned. These young plants may be protected before transplantation by a total or partial treatment by immersion. Preferably "plant propagation material” is understood to denote seeds.
  • the compounds of formula I can be used in unmodified form or, preferably, together with carriers and adjuvants conventionally employed in the art of formulation.
  • the invention also relates to compositions for controlling and protecting against phytopathogenic microorganisms, comprising a compound of formula I and an inert carrier, and to a method of controlling or preventing infestation of useful plants by phytopathogenic microorganisms, wherein a composition, comprising a compound of formula I as acitve ingredient and an inert carrier, is applied to the plants, to parts thereof or the locus thereof.
  • compositions are conveniently formulated in known manner to emulsifiable concentrates, coatable pastes, directly sprayable or dilutable solutions, dilute emulsions, wettable powders, soluble powders, dusts, granulates, and also encapsulations e.g. in polymeric substances.
  • the methods of application such as spraying, atomising, dusting, scattering, coating or pouring, are chosen in accordance with the intended objectives and the prevailing circumstances.
  • the compositions may also contain further adjuvants such as stabilizers, antifoams, viscosity regulators, binders or tackifiers as well as fertilizers, micronutrient donors or other formulations for obtaining special effects.
  • Suitable carriers and adjuvants can be solid or liquid and are substances useful in formulation technology, e.g. natural or regenerated mineral substances, solvents, dispersants, wetting agents, tackifiers, thickeners, binders or fertilizers. Such carriers are for example described in WO 97/33890 .
  • the compounds of formula I or compositions comprising a compound of formula I as acitve ingredient and an inert carrier, can be applied to the locus of the plant or plant to be treated, simultaneously or in succession with further compounds.
  • further compounds can be e.g. fertilizers or micronutrient donors or other preparations which influence the growth of plants. They can also be selective herbicides as well as insecticides, fungicides, bactericides, nematicides, molluscicides or mixtures of several of these preparations, if desired together with further carriers, surfactants or application promoting adjuvants customarily employed in the art of formulation.
  • a preferred method of applying a compound of formula I, or a composition, comprising a compound of formula I as active ingredient and an inert carrier is foliar application.
  • the frequency of application and the rate of application will depend on the risk of infestation by the corresponding pathogen.
  • the compounds of formula I can also penetrate the plant through the roots via the soil (systemic action) by drenching the locus of the plant with a liquid formulation, or by applying the compounds in solid form to the soil, e.g. in granular form (soil application). In crops of water rice such granulates can be applied to the flooded rice field.
  • the compounds of formula I may also be applied to seeds (coating) by impregnating the seeds or tubers either with a liquid formulation of the fungicide or coating them with a solid formulation.
  • a formulation i.e. a composition comprising the compound of formula I and, if desired, a solid or liquid adjuvant, is prepared in a known manner, typically by intimately mixing and/or grinding the compound with extenders, for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • extenders for example solvents, solid carriers and, optionally, surface-active compounds (surfactants).
  • the agrochemical formulations will usually contain from 0.1 to 99% by weight, preferably from 0.1 to 95% by weight, of the compound of formula I, 99.9 to 1% by weight, preferably 99.8 to 5% by weight, of a solid or liquid adjuvant, and from 0 to 25% by weight, preferably from 0.1 to 25% by weight, of a surfactant.
  • Advantageous rates of application are normally from 5g to 2kg of active ingredient (a.i.) per hectare (ha), preferably from 10g to 1 kg a.i./ha, most preferably from 20g to 600g a.i./ha.
  • convenient rates of application are from 10mg to 1g of active substance per kg of seeds.
  • the rate of application for the desired action can be determined by experiments. It depends for example on the type of action, the developmental stage of the useful plant, and on the application (location, timing, application method) and can, owing to these parameters, vary within wide limits.
  • the compounds of formula (I), or a pharmaceutical salt thereof, described above may also have an advantageous spectrum of activity for the treatment and/or prevention of microbial infection in an animal.
  • Animal can be any animal, for example, insect, mammal, reptile, fish, amphibian, preferably mammal, most preferably human.
  • Treatment means the use on an animal which has microbial infection in order to reduce or slow or stop the increase or spread of the infection, or to reduce the infection or to cure the infection.
  • prevention means the use on an animal which has no apparent signs of microbial infection in order to prevent any future infection, or to reduce or slow the increase or spread of any future infection.
  • a compound of formula (I) in the manufacture of a medicament for use in the treatment and/or prevention of microbial infection in an animal.
  • a compound of formula (I) as a pharmaceutical agent.
  • a compound of formula (I) as an antimicrobial agent in the treatment of an animal.
  • a pharmaceutical composition comprising as an active ingredient a compound of formula (I), or a pharmaceutically acceptable salt thereof, and a pharmaceutically acceptable diluent or carrier. This composition can be used for the treatment and/or prevention of antimicrobial infection in an animal.
  • This pharmaceutical composition can be in a form suitable for oral administration, such as tablet, lozenges, hard capsules, aqueous suspensions, oily suspensions, emulsions dispersible powders, dispersible granules, syrups and elixirs.
  • this pharmaceutical composition can be in a form suitable for topical application, such as a spray, a cream or lotion.
  • this pharmaceutical composition can be in a form suitable for parenteral administration, for example injection.
  • this pharmaceutical composition can be in inhalable form, such as an aerosol spray.
  • the compounds of formula (I) may be effective against various microbial species able to cause a microbial infection in an animal.
  • microbial species are those causing Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger, those causing Blastomycosis such as Blastomyces dermatitidis; those causing Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilosis, C. krusei and C.
  • Aspergillosis such as Aspergillus fumigatus, A. flavus, A. terrus, A. nidulans and A. niger
  • Blastomycosis such as Blastomyces dermatitidis
  • Candidiasis such as Candida albicans, C. glabrata, C. tropicalis, C. parapsilos
  • Fusarium Spp such as Fusarium oxysporum and Fusarium solani and Scedosporium Spp such as Scedosporium apiospermum and Scedosporium prolificans .
  • Microsporum Spp Trichophyton Spp, Epidermophyton Spp, Mucor Spp, Sporothorix Spp, Phialophora Spp, Cladosporium Spp, Petriellidium spp, Paracoccidioides Spp and Histoplasma Spp.
  • Example P1 Preparation of trans 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ⁇ 1-[2-(2-chloro-phenyl)-cyclopropyl]-ethyl ⁇ -methoxy-amide (compound 1.011 diastereomere A):
  • Example P2 Preparation of trans 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ⁇ 1-[2-(2-chloro-phenyl)-cyclopropyl]-ethyl ⁇ -methoxy-amide (compound 1.011 diastereomere B):
  • Example P4 Preparation of trans-3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ⁇ 1-[2-(2,4-dichlorophenyl)-cyclopropyl]-ethyl ⁇ -methoxy-amide (compound 1.018 diastereomere B):
  • Example P5 Preparation of trans 3-difluoromethyl-1-methyl-1H-pyrazole-4-carboxylic acid ⁇ 1-[2-(2-chloro-6-fluoro-phenyl)-cyclopropyl]-ethyl ⁇ -methoxy-amide (compound 1.027):
  • reaction mixture was stirred for 0.5 hours, poured onto ice water (100 ml) and extracted with ether (3 x 25 ml). Combined organic layers were washed with water, brine and dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by flash chromatography over silica gel (25 g) (eluent: n-hexane/ethyl acetate 10:1) to afford 0.33 g (62 % of theory) of trans 1-[2-(2,4-dichloro-phenyl)-cyclopropyl]-ethyanone in form of an oil.
  • reaction mixture was stirred for 0.5 hours, poured onto ice water (10 ml) and extracted with ether (3 x 5 ml). Combined organic layers were washed with water, brine and dried over anhydrous sodium sulfate. The solvent was removed in vacuo and the residue was purified by flash chromatography over silica gel (25 g) (eluent: n-hexane/ethyl acetate 20:1) to afford 60 mg (57 % of theory) of trans 1-[2-(2,4,6-trichloro-phenyl)-cyclopropyl]-ethyanone in form of a pale yellow liquid.
  • A is selected from the groups consisting of A 1 , A 2 , and A 3 B is B 1 ,
  • Tables 1 to 3 which follow the Table Y below, comprises 95 compounds of formula (Ia) in which R 5 , R 8 , B, R 11 , R 12 and R 13 have the values given in Table Y and A has the value given in the relevant Table 1 to 3.
  • Table 1 corresponds to Table Y when Y is 1 and A has the value given under the Table 1 heading
  • Table 2 corresponds to Table Y when Y is 2 and A has the value given under the Table 2 heading, and so on for Table 3.
  • Table Y (“M" means the methyl group): Cpd No.
  • Table 1 provides 51 compounds of formula (Ia), wherein A is A 1 and R 5 , R 8 , B, R 11 , R 12 , and R 13 are as defined in Table Y.
  • compound 1.034 has the following structure:
  • Table 2 provides 51 compounds of formula (Ia), wherein A is A 2 and R 5 , R 8 , B, R 11 , R 12 , and R 13 are as defined in Table Y.
  • Table 3 provides 51 compounds of formula (Ia), wherein A is A 3 and R 5 , R 8 , B, R 11 , R 12 , and R 13 are as defined in Table Y.
  • Table 4 which follow the Table Y above, comprises 51 compounds of formula (IIb) in which R 5 , R 8 , B, R 11 , R 12 , and R 13 have the values given in Table Y.
  • Table 4 provides 51 compounds of formula (IIb) wherein R 5 , R 8 , B, R 11 , R 12 , and R 13 are as defined In Table Y.
  • Table 5 shows selected melting point and selected NMR data for compounds of Table 1 to 3.
  • CDCl 3 is used as the solvent for NMR measurements, unless otherwise stated. If a mixture of solvents is present, this is indicated as, for example: CDCl 3 /d 6 -DMSO). No attempt is made to list all characterising data in all cases.
  • a 384/386 oil 1.011 1.02-1.07(m,1H);1.10-1.15(m,1H);1.44 (d,3H);1.48-1.55(m,1 H);2.36-2.42(m,1 H); 3.65(s,3H);3.96(s,3H);4.09-4.17(m,1H); 6.88-6.90(m,1H);7.06-7.17(m,2H); 7.09+7.23+7.37(t,1H);7.27-7.31(m,1H); 7.86(s,1H).
  • a 418/420/422 133-135 1.018 1.02-1.14(m,2H);1.43-1.48(d,3H);1.43-1.58(m,1H);2.28-2.37(m,1H);3.65(1s,3H); 3.96(s;3H);4.05-4.17(m,1H);6.79-6.83 (d,1H);7.04-7.43(t,1H,CHF 2 );7.12-7.16 (dd,1H);7.31-7.33(d,1H); 7.95(s,1H).
  • mixture 402/404 oil 1.028 0.81-1.68(m,6H);1.78-2.02(m,1H);3.75+ 3.78(2s,3H);3.96+3.97(2s;3H);4.04-4.18 (m,1H);7.03-7.18(m,1H);7.22-7.29(m,2H); 7.89+7.93(2s,1H).
  • mixture 418/420/422 oil 1.034 0.80-1.70(m,6H);1.72-1.95(m,1H);3.75+3.78 (2s,3H);3.96+3.97(2s;3H);4.04-4.18+4.46 -4.55(m,1 H);7.03-7.42+7.06-7.48 (2t,1H,CHF 2 );7.24+7.26(2s,2H);7.89+ 7.93(2s,1H).
  • Example F-1.1 to F-1.2 Emulsifiable concentrates
  • Components F-1.1 F-1.2 compound of Tables 1-3 25% 50% calcium dodecylbenzenesulfonate 5% 6% castor oil polyethylene glycol ether (36 mol ethylenoxy units) 5% - tributylphenolpolyethylene glycol ether (30 mol ethylenoxy units) - 4% cyclohexanone - 20% xylene mixture 65% 20%
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • Example F-2 Emulsifiable concentrate
  • Components F-2 compound of Tables 1-3 10% octylphenolpolyethylene glycol ether (4 to 5 mol ethylenoxy units) 3% calcium dodecylbenzenesulfonate 3% castor oil polyglycol ether (36 mol ethylenoxy units) 4% cyclohexanone 30% xylene mixture 50%
  • Emulsions of any desired concentration can be prepared by diluting such concentrates with water.
  • the solutions are suitable for use in the form of microdrops.
  • the novel compound is dissolved in dichloromethane, the solution is sprayed onto the carrier and the solvent is then removed by distillation under vacuum.
  • Example F7 Flowable concentrate for seed treatment
  • the finely ground active ingredient is intimately mixed with the adjuvants, giving a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • a suspension concentrate from which suspensions of any desired dilution can be obtained by dilution with water.
  • living plants as well as plant propagation material can be treated and protected against infestation by microorganisms, by spraying, pouring or immersion.
  • Example B-1 Action against Botrytis cinerea - fungal growth assay
  • Example B-2 Action against Mycosphaerella arachidis (early leaf spot of groundnut; Cercospora arachidicola [anamorph])- fungal growth assay
  • Example B-3 Action against Septoria tritici - fungal growth assay
  • Example B-4 Action against Monographella nivalis (anamorph: Fusarium nivale, Microdochium nivale; Snow mould) - fungal growth assay
  • Example B-5 Action against Erysiphe graminis f.sp. tritici (wheat powdery mildew)
  • Wheat leaf segments were placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound was assessed 7 days after inoculation as preventive fungicidal activity.
  • Example B-6 Protective action against Puccinia recondita (brown rust) on wheat
  • Wheat leaf segments were placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound was assessed 8 days after inoculation as preventive fungicidal activity.
  • Example B-7 Curative action against Puccinia recondita (brown rust) on wheat
  • Example B-8 Action against Pyrenophora teres (net blotch) on barley
  • Barley leaf segments were placed on agar in multiwell plates (24-well format) and sprayed with test solutions (0.02% active ingredient). After drying, the leaf disks were inoculated with a spore suspension of the fungus. After appropriate incubation the activity of a compound was assessed 4 days after inoculation as preventive fungicidal activity.
  • Example B-9 Action against Rhizoctonia solani - fungal growth assay

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Plural Heterocyclic Compounds (AREA)

Claims (8)

  1. Verbindung der Formel (I)
    Figure imgb0047
     wobei
    R1 für C1-C4-Alkyl oder C1-C4-Halogenalkyl steht;
    R2 für C1-C4-Alkyl steht;
    R3 für Wasserstoff oder Halogen steht;
    R4 für Wasserstoff, C1-C4-Alkyl oder C1-C4-Halogenalkyl steht;
    R5 und R6 unabhängig voneinander für Wasserstoff, Halogen, C1-C4-Alkyl oder C1-C4-Halogenalkyl stehen;
    R7, R8, R9 und R10 unabhängig voneinander für Wasserstoff, Halogen, C1-C6-Alkyl, C2-C6-Alkenyl, C3-C6-Alkinyl oder C1-C4-Alkoxy stehen;
    B für B1 steht
    Figure imgb0048
     wobei
    R11, R12 und R13 unabhängig voneinander für Wasserstoff, Halogen oder C1-C6-Alkyl stehen;
    und agrochemisch unbedenkliche Salze/Stereoisomere/Diastereoisomere/Enantiomere/Tautomere und N-Oxide dieser Verbindungen.
  2. Verbindung der Formel I nach Anspruch 1, wobei R1 für C1-C4-Halogenalkyl steht;
    R2 für C1-C4-Alkyl steht;
    R3 für Wasserstoff steht;
    R4 für C1-C4-Alkyl steht;
    R5 für Wasserstoff oder C1-C4-Alkyl steht;
    R6 für Wasserstoff steht;
    R7 für Wasserstoff, C1-C4-Alkyl oder Halogen steht;
    R8 für Wasserstoff, C1-C4-Alkyl oder Halogen steht;
    R9 für Wasserstoff, C1-C4-Alkyl oder Halogen steht;
    R10 für Wasserstoff, C1-C4-Alkyl oder Halogen steht;
    R11, R12 und R13 unabhängig voneinander für Wasserstoff oder Halogen stehen.
  3. Verbindung der Formel I nach Anspruch 2, wobei R5 für Methyl steht.
  4. Verbindung der Formel I nach Anspruch 1, wobei R1 für Difluormethyl steht;
    R2 für Methyl steht;
    R3 für Wasserstoff steht;
    R4 für Methyl steht;
    R5 für Wasserstoff oder Methyl steht;
    R6 für Wasserstoff steht;
    R7 für Wasserstoff, Methoxy oder Chlor steht; und
    R8, R9 und R10 für Wasserstoff stehen.
  5. Verbindung der Formel I nach Anspruch 1, wobei R1 für Difluormethyl oder Trifluormethyl steht;
    R2 für Methyl steht;
    R3 für Wasserstoff steht;
    R4 für Methyl steht;
    R5 für Wasserstoff, Methyl oder Ethyl steht; und
    R6, R7, R8, R9 und R10 für Wasserstoff stehen.
  6. Verbindung der Formel I nach Anspruch 1, wobei R1 für C1-C4-Halogenalkyl steht;
    R2 für C1-C4-Alkyl steht;
    R3 für Wasserstoff steht;
    R4 für C1-C4-Alkyl steht;
    R5 für C1-C4-Alkyl steht;
    R6, R7, R8, R9 und R10 für Wasserstoff stehen;
    R11, R12 und R13 unabhängig voneinander für Wasserstoff oder Halogen stehen.
  7. Verfahren zur Bekämpfung von phytopathogenen Mikroorganismen oder zum Verhindern des Befalls nützlicher Pflanzen durch phytopathogene Mikroorganismen, wobei auf die Pflanzen, auf Teile davon oder den Standort davon eine Verbindung der Formel I nach Anspruch 1 oder eine diese Verbindung als Wirkstoff enthaltende Zusammensetzung ausgebracht wird.
  8. Zusammensetzung zur Bekämpfung von phytopathogenen Mikroorganismen und zum Schutz gegen phytopathogene Mikroorganismen, umfassend eine Verbindung der Formel I nach Anspruch 1.
EP10765439.4A 2009-10-16 2010-10-14 Neue mikrobiozide Active EP2488501B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP10765439.4A EP2488501B1 (de) 2009-10-16 2010-10-14 Neue mikrobiozide

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP09173257 2009-10-16
EP10765439.4A EP2488501B1 (de) 2009-10-16 2010-10-14 Neue mikrobiozide
PCT/EP2010/065371 WO2011045355A1 (en) 2009-10-16 2010-10-14 Novel microbiocides

Publications (2)

Publication Number Publication Date
EP2488501A1 EP2488501A1 (de) 2012-08-22
EP2488501B1 true EP2488501B1 (de) 2014-04-30

Family

ID=43086435

Family Applications (1)

Application Number Title Priority Date Filing Date
EP10765439.4A Active EP2488501B1 (de) 2009-10-16 2010-10-14 Neue mikrobiozide

Country Status (7)

Country Link
US (1) US8357635B2 (de)
EP (1) EP2488501B1 (de)
CN (1) CN102574808A (de)
BR (1) BR112012008952A2 (de)
ES (1) ES2475737T3 (de)
IN (1) IN2012DN02698A (de)
WO (1) WO2011045355A1 (de)

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8999956B2 (en) 2010-06-03 2015-04-07 Bayer Intellectual Property Gmbh N-[(het)arylalkyl)] pyrazole(thio)carboxamides and their heterosubstituted analogues
WO2012027140A2 (en) * 2010-08-27 2012-03-01 Anitox Corporation Antimicrobial formulation
HUE033375T2 (en) 2011-10-20 2017-11-28 Anitox Corp Antimicrobial formulations with pelargonic acid
CN118561756A (zh) * 2023-02-21 2024-08-30 帕潘纳(北京)科技有限公司 一种吡唑甲酰胺类化合物及其应用

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3541106A (en) * 1967-12-28 1970-11-17 Velsicol Chemical Corp Certain substituted n-phenyl-n-hydroxy-nicotinamides,the corresponding isonicotinamines and picolinamides
ATA937274A (de) 1973-12-17 1978-02-15 Thomae Gmbh Dr K Verfahren zur herstellung neuer araliphatischer ketone
DE3415138A1 (de) * 1984-04-21 1985-10-31 Basf Ag, 6700 Ludwigshafen N-(azolylcarbamoyl)-hydroxylamine und diese enthaltende fungizide
CA1340685C (en) 1988-07-29 1999-07-27 Frederick Meins Dna sequences encoding polypeptides having beta-1,3-glucanase activity
DE69034081T2 (de) 1989-03-24 2004-02-12 Syngenta Participations Ag Krankheitsresistente transgene Pflanze
US5120752A (en) * 1989-12-28 1992-06-09 Abbott Laboratories Cyclopropyl derivative lipoxygenase inhibitors
US5639949A (en) 1990-08-20 1997-06-17 Ciba-Geigy Corporation Genes for the synthesis of antipathogenic substances
JP3007138B2 (ja) * 1990-11-27 2000-02-07 ファイザー製薬株式会社 新規なヒドロキサム酸とｎ―ヒドロキシ尿素誘導体およびそれらの組成物
US5223526A (en) 1991-12-06 1993-06-29 Monsanto Company Pyrazole carboxanilide fungicides and use
DE4231517A1 (de) 1992-09-21 1994-03-24 Basf Ag Carbonsäureanilide, Verfahren zu ihrer Herstellung und sie enthaltende Mittel zur Bekämpfung von Schadpilzen
CZ288498A3 (cs) 1996-03-11 1998-12-16 Novartis Ag Deriváty pyrimidin-4-onu jako pesticidní látky, způsob jejich přípravy a agrochemické prostředky, které je obsahují
GB9817548D0 (en) 1998-08-12 1998-10-07 Novartis Ag Organic compounds
WO2001059584A1 (en) 2000-02-10 2001-08-16 University Of Washington Practical network support for ip traceback
CA2426033A1 (en) 2000-11-08 2002-05-16 Syngenta Participations Ag Pyrrolcarboxamides and pyrrolcarbothioamides and their agrochemical uses
JP4643441B2 (ja) 2002-08-22 2011-03-02 シンジェンタ パーティシペーションズ アクチェンゲゼルシャフト 化合物
BRPI0712027B1 (pt) 2006-05-18 2015-12-15 Syngenta Ltd compostos microbiocidas, método e composição para controle e proteção contra microorganismos fitopatogênicos

Also Published As

Publication number Publication date
ES2475737T3 (es) 2014-07-11
EP2488501A1 (de) 2012-08-22
US20120202867A1 (en) 2012-08-09
CN102574808A (zh) 2012-07-11
IN2012DN02698A (de) 2015-09-04
WO2011045355A1 (en) 2011-04-21
US8357635B2 (en) 2013-01-22
BR112012008952A2 (pt) 2015-09-22

Similar Documents

Publication Publication Date Title
US8258169B2 (en) Pyrazole-4-N-alkoxycarboxamides as microbiocides
EP2155686B1 (de) Pyrazolcarbonsäureamide als mikrobiozide
EP2576515B1 (de) Pyrazolcarboxamidderivate und ihre Verwendung als Mikrobiozide
US20110092558A1 (en) Novel microbiocides
WO2010106071A1 (en) N-hydroxy-l-methyl-lh-pyrazole-4-carboxamide derivatives and their use as microbiocides
EP2488501B1 (de) Neue mikrobiozide
WO2009127722A1 (en) Novel microbiocides
US8357634B2 (en) N-alkoxycarboxamides and their use as microbiocides
EP2678328B1 (de) Neue carboxamid-mikrobiozide
EP2451799B1 (de) Neue mikrobiozide
EP2536692B1 (de) Pyrazol-mikrobiozide
WO2009127726A1 (en) Novel microbiocides
EP2661426A1 (de) Pyrazol-4-yl-carboxamidderivate als mikrobiozide

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20120316

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20130417

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20140205

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: CH

Ref legal event code: EP

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 665029

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140515

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602010015653

Country of ref document: DE

Effective date: 20140612

REG Reference to a national code

Ref country code: NL

Ref legal event code: T3

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2475737

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20140711

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 665029

Country of ref document: AT

Kind code of ref document: T

Effective date: 20140430

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140731

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140730

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140830

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140730

REG Reference to a national code

Ref country code: GB

Ref legal event code: 732E

Free format text: REGISTERED BETWEEN 20141023 AND 20141029

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140901

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: BE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010015653

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20150202

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602010015653

Country of ref document: DE

Effective date: 20150202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: LU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20141014

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 6

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20141014

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20101014

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 7

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 8

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 9

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20140430

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20220916

Year of fee payment: 13

Ref country code: GB

Payment date: 20220914

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20220916

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: IT

Payment date: 20221014

Year of fee payment: 13

Ref country code: ES

Payment date: 20221101

Year of fee payment: 13

Ref country code: DE

Payment date: 20220627

Year of fee payment: 13

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 20221101

Year of fee payment: 13

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602010015653

Country of ref document: DE

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

REG Reference to a national code

Ref country code: NL

Ref legal event code: MM

Effective date: 20231101

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20231014

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231014

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231031

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231101

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231101

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231014

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231031

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20240501

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20231031